On the interaction of stochastic forcing and regime dynamics

Stochastic forcing can, sometimes, stabilise atmospheric regime dynamics, increasing their persistence. This counter-intuitive effect has been observed in geophysical models of varying complexity, and here we investigate the mechanisms underlying stochastic regime dynamics in a conceptual model. We use a six-mode truncation of a barotropic β-plane model, featuring transitions between analogues of zonal and blocked flow conditions, and identify mechanisms similar to those seen previously in work on low-dimensional random maps. Namely, we show that a geometric mechanism, here relating to monotonic instability growth, allows for asymmetric action of symmetric perturbations on regime lifetime and that random scattering can “trap” the flow in more stable regions of phase space. We comment on the implications for understanding more complex atmospheric systems

Structures and Reactivity Patterns of Group 9 Metallocorroles

Group 9 metallocorroles 1-M(PPh_3) and 1-M(py)_2 [M = Co(III), Rh(III), Ir(III); 1 denotes the trianion of 5,10,15-tris-pentafluorophenylcorrole] have been fully characterized by structural, spectroscopic, and electrochemical methods. Crystal structure analyses reveal that average metal−N(pyrrole) bond lengths of the bis-pyridine metal(III) complexes increase from Co (1.886 Å) to Rh (1.957 Å)/Ir (1.963 Å); and the average metal−N(pyridine) bond lengths also increase from Co (1.995 Å) to Rh (2.065 Å)/Ir (2.059 Å). Ligand affinities for 1-M(PPh_3) axial coordination sites increase dramatically in the order 1-Co(PPh_3) < 1-Rh(PPh_3) < 1-Ir(PPh_3). There is a surprising invariance in the M(+/0) reduction potentials within the five- and six-coordinate corrole series, and even between them; the average M(+/0) potential of 1-M(PPh_3) is 0.78 V vs Ag/AgCl in CH_2Cl_2 solution, whereas that of 1-M(py)_2 is 0.70 V under the same conditions. Electronic structures of one-electron-oxidized 1-M(py)_2 complexes have been assigned by analysis of electron paramagnetic resonance spectroscopic measurements: oxidation is corrole-centered for 1-Co(py)_2 (g = 2.008) and 1-Rh(py)_2 (g = 2.003), and metal-centered for 1-Ir(tma)_2 (g_(zz) = 2.489, g_(yy) = 2.010, g_(xx) = 1.884, g_(av) = 2.128) and 1-Ir(py)_2 (g_(zz) = 2.401, g_(yy) = 2.000, g_(xx) = 1.937, g_(av) = 2.113)

Outer-Sphere Effects on Reduction Potentials of Copper Sites in Proteins: The Curious Case of High Potential Type 2 C112D/M121E Pseudomonas aeruginosa Azurin

Redox and spectroscopic (electronic absorption, multifrequency electron paramagnetic resonance (EPR), and X-ray absorption) properties together with X-ray crystal structures are reported for the type 2 Cu^(II) C112D/M121E variant of Pseudomonas aeruginosa azurin. The results suggest that Cu^(II) is constrained from interaction with the proximal glutamate; this structural frustration implies a “rack” mechanism for the 290 mV (vs NHE) reduction potential measured at neutral pH. At high pH (~9), hydrogen bonding in the outer coordination sphere is perturbed to allow axial glutamate ligation to Cu^(II), with a decrease in potential to 119 mV. These results highlight the role played by outer-sphere interactions, and the structural constraints they impose, in determining the redox behavior of transition metal protein cofactors

Strategy for Mitigating Collision Between Landsat-5 and the Afternoon Constellation

The NASA Goddard Space Flight Center Earth Science Mission Operations project, the French space agency Centre National d tudes Spatiales, the Argentinian space agency Comisi n Nacional de Actividades Espaciales, and the United States Geological Survey all operate spacecraft in sun-synchronous frozen orbits. The orbits are planned to not place any of the spacecraft at risk of colliding with another. However, evolution of these orbits over time has com-promised the safe interaction between Landsat-5 and the Afternoon Constella-tion. This paper analyzes the interactions between the Landsat-5 spacecraft and the Afternoon Constellation members over a period of 6 years, describing the current risk and plan to mitigate collisions in the future

Gamma-ray Bursts, Classified Physically

From Galactic binary sources, to extragalactic magnetized neutron stars, to long-duration GRBs without associated supernovae, the types of sources we now believe capable of producing bursts of gamma-rays continues to grow apace. With this emergent diversity comes the recognition that the traditional (and newly formulated) high-energy observables used for identifying sub-classes does not provide an adequate one-to-one mapping to progenitors. The popular classification of some > 100 sec duration GRBs as ``short bursts'' is not only an unpalatable retronym and syntactically oxymoronic but highlights the difficultly of using what was once a purely phenomenological classification to encode our understanding of the physics that gives rise to the events. Here we propose a physically based classification scheme designed to coexist with the phenomenological system already in place and argue for its utility and necessity.Comment: 6 pages, 3 figures. Slightly expanded version of solicited paper to be published in the Proceedings of ''Gamma Ray Bursts 2007,'' Santa Fe, New Mexico, November 5-9. Edited by E. E. Fenimore, M. Galassi, D. Palme

Crystal structure of bis[1-(2-hydroxyethyl)-2-methyl-5-nitro- 1H-imidazole-κN3]silver(I) tetrafluoridoborate methanol monosolvate

1-(2-Hydroxyethyl)-2-methyl-5-nitro-1Η-imidazole (metronidazole, MET) is a medication that is used to treat infections by a variety of anaerobic organisms, but there are relatively few reports of the structures of metal compounds that exhibit coordination of metronidazole. We have demonstrated that MET reacts with AgBF4 to give [Ag(MET)2]BF4•CH3OH, in which the AgI cation is coordinated by two MET ligands with a trans arrangement. The structure of [Ag(MET)2]BF4 exhibits some interesting differences from its nitrate counterpart, [Ag(MET)2]NO3 [Fun et al. (2008). Acta Cryst. E64, m668]. For instance, although the two MET ligands of both [Ag(MET)2]BF4 and [Ag(MET)2]NO3 are almost coplanar, the former compound has an anti-like geometry with a molecular inversion center, but the latter has a syn-like arrangement. In the crystal, the BF4− anion is linked by an O—H•••F hydrogen bond to the methanol solvent molecule, which is, in turn, linked to the cation by an O— H•••O hydrogen bond; the components of the structure are linked by O—H•••O hydrogen bonds, forming chains along [001]. One of the MET ligands and the BF4 − anion are disordered over two sets of sites with ratios of refined occupancies 0.501 (17):0.499 (17) and 0.539 (19):0.461 (19), respectively

Iodinated Aluminum(III) Corroles with Long-Lived Triplet Excited States

The first reported iodination of a corrole leads to selective functionalization of the four C–H bonds on one pole of the macrocycle. An aluminum(III) complex of the tetraiodinated corrole, which exhibits red fluorescence, possesses a long-lived triplet excited state

Advanced Magnetic Resonance Imaging in Glioblastoma: A Review

INTRODUCTION In 2017, it is estimated that 26,070 patients will be diagnosed with a malignant primary brain tumor in the United States, with more than half having the diagnosis of glioblas- toma (GBM).1 Magnetic resonance imaging (MRI) is a widely utilized examination in the diagnosis and post-treatment management of patients with glioblastoma; standard modalities available from any clinical MRI scanner, including T1, T2, T2-FLAIR, and T1-contrast-enhanced (T1CE) sequences, provide critical clinical information. In the last decade, advanced imaging modalities are increasingly utilized to further charac- terize glioblastomas. These include multi-parametric MRI sequences, such as dynamic contrast enhancement (DCE), dynamic susceptibility contrast (DSC), diffusion tensor imaging (DTI), functional imaging, and spectroscopy (MRS), to further characterize glioblastomas, and significant efforts are ongoing to implement these advanced imaging modalities into improved clinical workflows and personalized therapy approaches. A contemporary review of standard and advanced MR imaging in clinical neuro-oncologic practice is presented